Super capacitor structure and the manufacture thereof

ABSTRACT

Disclosed is a super capacitor and method of manufacture thereof. This invention relates to a solid state super capacitor comprising a solid state polymer electrolyte and a modified carbonaceous electrode. Said modified carbonaceous electrode comprises a conductive carbonaceous material covered with active ingredients. Said modified carbonaceous electrode and said solid state polymer electrolyte are layered on top of each other to form a sandwich-like structure. Said super capacitor performs much better than known super capacitor comprising liquid or gel-form electrolytes. Said super capacitor has higher conductivity, therefore can be manufactured without a current collector. Since said super capacitor contains solid state polymer electrolyte, the method of manufacturing said super capacitor is more environmentally friendly and has a higher safety level.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 13/418,342, filed on Mar. 12, 2012, which is incorporated byreference, and which claims the benefit of Taiwanese Patent ApplicationNo. 100135833, filed on Oct. 4, 2011, under 35 U.S.C. §119. Each of theabove applications is incorporated by reference herein.

FIELD OF THE INVENTION

The present invention generally relates to a super capacitor, and moreparticularly to a super capacitor structure and method of manufacturethereof.

BACKGROUND OF THE INVENTION

Super capacitors are usually referred to Electric Double LayerCapacitor, EDLC, as shown in FIG. 1, which includes components such asan electrode 1 containing a metallic current collector 2, a liquid orgel-like electrolyte 3, a separator 4 and a conductive pad 20. The EDLCcan be rapidly charged and discharged through the charge adsorptioneffect of the electric double layer on the surface of the electrode.Super capacitors have a capacity as high as 1˜10³F or more. The chargeand discharge power ratio of super capacitors is much higher than thatof the secondary batteries (Lithium battery or lead-acid battery), andthe level of transient output current of super capacitors is extremelyhigh. However, the total storage capacity of super capacitors isinferior to secondary batteries. Super capacitors are applied primarilyin electronic industry, followed by energy or green-energy industry andtransportation industry. Super capacitors for commercial purpose havebeen successful for the past 30 years. However, the demand was low inearly stage due to the high price. With the improvement in function andperformance, lower price range, and fast increase of applications in thelast decade, now is the best time to develop and produce supercapacitors. Nevertheless, super capacitors currently on the market haveproblems such as high resistance, complex manufacturing process, andcontain liquid or gel-like electrolytes.

TABLE 1 Problems of super capacitors currently on the market. Currentlyknown Item super capacitors Problem Electrode Activated carbon,Insufficient conductivity. carbon black, Flat electrode, lower specificmetal-oxides, and surface area. conductive polymeric adhesives.Electrolyte Liquid or gel-like Possess chemical toxicity, under roomtemperature. flammable, potential leakage Water based or organichazards, and complex electrolyte. manufacture procedures. Unable tofunction under extremely high or low temperature. Other parts Separator,current Require metallic current collector, conductive collector due toinsufficient pad conductivity of the electrode. Require separator due tothe usage of liquid or gel-like electrolyte. Manufacturing Factorylayout and Require expensive clean room process and equipment are andfactory design. equipment expensive Require costly equipment toaccommodate the manufacture of liquid or gel-like electrolyte.

SUMMARY OF THE INVENTION

To overcome the aforementioned drawbacks, embodiments of the inventiondisclose a super capacitor structure and method of manufacture thereof.

The present invention employs a modified carbonaceous electrode and asolid polymer electrolyte. A super capacitor structure comprising incontiguity a modified carbonaceous electrode, a solid polymerelectrolyte interposed between the modified carbonaceous electrode, anda conductive pad electrically connected at least a portion of themodified carbonaceous electrode characterized in that the modifiedcarbonaceous electrode comprises an active material in athree-dimensional state. The present invention does not require aseparator since the present invention does not employ liquid or gel-likeelectrolyte. The present invention does not require a metallic currentcollector because the modified carbonaceous electrode has a highconductivity. The super capacitor structure is very different form thesuper capacitors currently known on the market. A sample of the presentinvention was tested to have a power ratio density of 2˜10 kW/kg, and anenergy ratio of 3˜20 Wh/kg. The test results indicate that the powerratio density of the present invention is about the same as supercapacitors currently on the market, however the energy density is higherthan that of the super capacitors currently known.

The present invention uses solid polymeric electrolyte, this featurehelps to simplify the manufacturing procedures and eliminate issuesconcerning toxicity and fire hazard. The present invention is safer touse and easier to produce compared with previously known supercapacitors that employ liquid or gel-like electrolytes. Moreover, themanufacturing procedures produce lesser toxic or chemical waste and theproduct of the procedures is not easy to explode. The present inventionfeatures better performances, lower cost, and the production process issafer and more environmental friendly. The following table indicates thefeatures of the present invention compared with super capacitorscurrently on the market:

TABLE 2 Comparisons between the present invention and the currentlyknown super capacitors Currently known Features of the Item supercapacitors Present invention present invention Electrode Activatedcarbon, Special carbon structure Modified materials carbon black, metal-and active materials carbonaceous oxides, and electrode conductivepolymeric High conductivity adhesives. High specific surface areaelectrolyte Liquid or gel-like Solid polymer No chemical toxicity, underroom electrolyte not easy to catch on temperature. fire, simplifiedWater based or manufacturing organic electrolyte. procedure Other partsSeparator, current Conductive pad Does not require collector, conductiveseparator or current pad collector Manufacturing Factory layout andSimplified Easier to set up a process and equipment are manufacturingprocess factory equipment expensive Cost Expensive hardware Lesshardware required, Lesser investment on and procedures cheaperproduction money and equipment process Product Better charge and As goodas or better than properties discharge super capacitors performancecurrently known Product safety Potential fire hazard Raise no suchconcerns Safer to use and leakage possibilities of the electrolyte

As shown in FIG. 2, the present invention discloses a super capacitorstructure comprising in contiguity a modified carbonaceous electrode, asolid polymer electrolyte interposed between the modified carbonaceouselectrode, and a conductive pad electrically connected at least aportion of the modified carbonaceous electrode characterized in that themodified carbonaceous electrode comprises an active material in athree-dimensional state. Wherein the modified carbonaceous electrode iscomprised of a conductive carbonaceous material containing an activematerial and has a high specific surface area. The conductive pad andthe modified carbonaceous electrode can also be arranged in layers or ina sandwich-like manner as shown in FIG. 3.

One embodiment of the structure of the modified carbonaceous electrodeis as indicated in FIG. 4. The conductive carbonaceous material can becomprised of a carbon cloth, a carbon felt, a carbon paper, a carbonfiber, a carbon pellet, or a carbon powder, that has a high conductivityand high specific surface area, wherein the active material isdistributed on extensive area within the vacant spaces and/or on thesurface of the conductive carbonaceous material. This method improvesthe performance of the disclosed super capacitor and elevates the chargetransport efficiency.

FIG. 4 shows that every fiber of the conductive carbonaceous material isevenly covered with the active material. The active material is selectedfrom electrostatic materials (such as: activated carbon powder, highlyconductive carbon black or carbon powder, or the mixture of polymericadhesives), Faradaic metal-oxides (such as: RuO₂, carbon black, or themixture of polymeric adhesives), or Faradaic conductive polymers (suchas doped type ion-conducting polymer, carbon black, or the mixture ofpolymeric adhesives). Since every fiber of the conductive carbonaceousmaterial is evenly covered with the active material, the active materialis hence distributed on the conductive carbonaceous material in athree-dimensional state. This helps to increase the total surface areacovered with the active material, and shortens the route for theelectron to enter and exit the electrode. These features remarkablyincrease the capacitance density (the capacity of the electrode in aunit area, F/cm²) and the electrical power ratio density (the dischargeelectrical power of the electrode per unit area, kW/cm²). Therefore, thesuper capacitor disclosed in the present invention performs much betterthan the super capacitors currently on the market.

Distributing the active material on every carbon fiber of the modifiedcarbonaceous electrode in a three-dimensional state or at least coverpart of the carbon fiber allows the electrode to become highlyconductive, high in mechanical stiffness, and high performance in chargeand discharge properties. Since the active material is evenlydistributed within the vacant spaces and/or on the surface of theconductive carbonaceous material, the route for electron to entering andexiting is shortened. The resistance and the interface resistance areboth very low, which is better than traditional super capacitors such astraditional active carbon electrodes, metal-oxide electrodes, orconductive polymers. Moreover, the modified carbonaceous electrode has ahigh conductivity; therefore the current enters and exits the supercapacitor directly without the help of a metal current collector. On theother hand, a metal current collector has to be connected to theelectrode in traditional super capacitors to collect the current andthen transfer the current in or out of the super capacitor via aconductive pad.

The present invention employs the art of producing the conductivecarbonaceous material and the technique of distributing the activematerial on the conductive carbonaceous material in a three-dimensionalstate, therefore gives the present invention improved features such ashigh specific capacity and high charge and discharge electric power.

The modified carbonaceous electrode can be made by a first manufacturingprocedure. The first manufacturing procedure uses a high quality carbonfabric as a conductive carbonaceous material (the carbon fabric ismanufactured according to U.S. Pat. No. 7,670,970B2 and U.S. Pat. No.7,927,575B2), wherein an active material is distributed on theconductive carbonaceous material. The conductive carbonaceous materialincludes a carbon cloth, a carbon felt, a carbon paper, a carbon fiber,a carbon pellet, or a carbon powder. The conductive carbonaceousmaterial has a sheet resistance of less than 200 Ω/sq, a density greaterthan 1.6 g/cm³, and a carbon content of greater than 65 wt %. The activematerial is distributed within the vacant spaces and/or on the surfaceof the conductive carbonaceous material by painting, tape casting,pressing, spraying, immersing, or the combination thereof. After abaking process within the temperature range of 60 to 400° C., the activematerial is hence solidified and the modified carbonaceous electrode isready for further manufacture.

The modified carbonaceous electrode can also be made by a secondmanufacturing procedure. The second procedure employs the carbon fiberas the conductive carbonaceous material. The carbon fiber is firstcovered with the active material and baked as described in the firstmanufacturing procedure. The carbon fiber is then weaved in a twodimensional, three dimensional, or more than three dimensional ways toform a carbon cloth and becomes the modified carbonaceous electrode. Thecarbon fiber carrying the active material can also be made into a carbonfelt by needle punching, or into a carbon paper or a carbon hand-sheetby paper making process. The carbon felt and the carbon paper cantherefore become the modified carbonaceous electrode. Both the first andthe second manufacturing procedures allow the active material to beevenly distributed on every surface or at least on part of the surfaceof each carbon fiber within or on the surface of the conductivecarbonaceous material.

The active material mentioned above includes a main component, aconductivity additive, and an adhesive. Wherein about 80 wt % or more ofthe active material is the main component. The main component includesNon-Faradaic or electrostatic components such as an activated carbon, ora Faradaic component or a Redox type component such as a metal-oxide(such as the powder of RuO₂, TiO₂, MnO₂, ZnO, NiO_(x), IrO₂ . . . etc.or the mixture thereof) or an ion-conducting polymer (such as: PEEK,SPEEK, PPV, PEKK, PEO, Nafion, PVA, PTFE, PPy, pMeT, PVDF, PEDOT, PANI,or the mixture thereof). The conductivity additive includes highlyconductive carbon powder such as a carbon black, a grapheme, or a carbonnanotube. About 5 wt % to no greater than 10 wt % of the active materialis the conductivity additive. The adhesive includes commonly knownadhesive polymers, or solid electrolytic polymers. About 10 wt % to nogreater than 15 wt % of the active material is the adhesive. Theion-conducting polymer mentioned above can serve as the Redox type maincomponent of the active material, as the solid polymer electrolytemembrane, or as the adhesive of the active material.

Reference for the chemical compounds mentioned in this specification isas follow:

PEEK: Polyether ether ketone

SPEEK: Sulfonated polyether ether ketone

PPV: Polyphenylene vinylene

PEKK: Poly (ether ketone ketone)

PEO: Polyethylene oxide

PVA: Polyvinyl alcohol

PTFE: Polytetrafluoroethylene

PEDOT: Polyethylenedioxythiophene

PANI: Polyaniline

PPy: Polypyrrole

Nafion: a sulfonated tetrafluoroethylene based fluoropolymer-copolymer.

Nafion is a product name of the U.S. company, DuPont.

PVDF: Polyvinylidene fluoride

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the structure of a currently known super capacitor (priorart).

FIG. 2 is a cross-sectional view of one embodiment of the presentinvention.

FIG. 3 is a cross-sectional view of another embodiment of the presentinvention.

FIG. 4 shows the structure of a modified carbonaceous electrode of thepresent invention.

FIG. 5 is a flow chart of the manufacturing procedure of the presentinvention.

FIG. 6 shows the first manufacturing procedure for the modifiedcarbonaceous electrode.

FIG. 7 shows the second manufacturing procedure for the modifiedcarbonaceous electrode.

FIG. 8 is the current-voltage diagram (CV diagram) of the supercapacitor comprising Sample A and the super capacitor comprising SampleB.

FIG. 9 shows the thermo gravimetric analysis (TGA) of Sample A.

FIG. 10 shows the result of the Constant Current Charge Discharge test(CCCD test) of Sample C.

FIG. 11 shows the result of the Cyclic life test of Sample D.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may best be understood by reference to thefollowing description in conjunction with the accompanying drawings.

One embodiment of the present invention is as shown in FIG. 2, FIG. 3and FIG. 4. A super capacitor structure 10 comprising in contiguity amodified carbonaceous electrode 30, a solid polymer electrolyte 40interposed between the modified carbonaceous electrode 30, and aconductive pad 20 electrically connected at least a portion of themodified carbonaceous electrode 30 characterized in that the modifiedcarbonaceous electrode 30 comprises an active material 32 in athree-dimensional state. The modified carbonaceous electrode 30 includesa conductive carbonaceous material 31 or highly conductive carbonfabrics such as a carbon cloth, a carbon felt, a carbon paper, a carbonfiber, a carbon pellet, or a carbon powder.

A first manufacturing procedure (see FIG. 6) for the modifiedcarbonaceous electrode 30 includes:

1. Preparing a precursor such as cloth, felt, or paper.

2. Turning the precursor into a conductive carbon material 31 throughhigh-temperature carbonization. The precursor of the conductive carbonmaterial 31 includes a carbon cloth, a carbon felt, a carbon paper, acarbon fiber, a carbon powder, or a carbon pellet.

3. Distributing the active material 32 onto the conductive carbonaceousmaterial 31.

4. Baking the conductive carbonaceous material 31.

5. Obtaining the modified carbonaceous electrode 30.

The conductive carbonaceous material 31 has a sheet resistance of lessthan 200 Ω/sq, a density greater than 1.6 g/cm³, a carbon content ofgreater than 65 wt %, and a specific surface area between 20 and 2000m²/g.

A second manufacturing procedure (see FIG. 7) for the modifiedcarbonaceous electrode 30 includes:

1. Preparing a precursor such as a fiber.

2. Turning the precursor into a conductive carbon fiber throughhigh-temperature carbonization. Wherein the conductive carbon fiberserves as the carbonaceous conductive material 31 in the secondmanufacturing procedure.

3. Distributing the active material 32 onto the conductive carbon fiber.

4. Baking the conductive carbon fiber.

5. Obtaining the modified carbonaceous electrode 30 from the conductivecarbon fiber by weaving, needle punching, or papermaking process.

The conductive carbon fiber has a resistivity lower than 5×10⁻² Ω/cm, adensity greater than 1.6 g/cm³, a carbon content greater than 65 wt %,and a specific surface area between 20 and 2000 m2/g.

In both the first and the second manufacturing procedures, the activematerial 32 is evenly distributed on at least part of the conductivecarbonaceous material 31 in a three-dimensional state. The method usedto distribute the active material 32 includes painting, tape casting,pressing, spraying, immersing, or the combination thereof. The activematerial 32 can be in a paste-like state. The active material 32 issolidified by baking within 60 to 400° C.

The active material 32 includes a main component, a conductivityadditive, and an adhesive. Wherein the main component is an activatedcarbon powder with a specific surface area between 20 and 2000 m²/g. Themain component includes PEEK, SPEEK, PPV, PEKK, PEO, Nafion, PVA, PTFE,PPy, pMeT, PVDF, PEDOT, PANI, or the combination thereof. The maincomponent may also include metal-oxide powder such as RuO₂, TiO₂, MnO₂,ZnO, NiO_(x), IrO₂, or the combination thereof. The adhesive includesPEEK, SPEEK, PPV, PEKK, PEO, Nafion, PVA, PTFE, PPy, pMeT, PVDF, PEDOT,PANI, or the combination thereof. The solid polymer electrolyte 40 ofthe super capacitor 10 includes an ion-conducting polymer or acombination of an ion-conductive polymer and an ionic compound. Thethickness of the solid polymer electrolyte 40 is between 0.5 and 50 μm.The ion-conducting polymer includes PEEK, SPEEK, PPV, PEKK, PEO, Nafion,PVA, PTFE, PPy, pMeT, PVDF, PEDOT, PANI, or the combination thereof. Theionic compound includes lithium hydroxide, lithium nitrate, lithiumtrifluoromethyl sulfur trioxide, or the combination thereof.

A second embodiment of the present invention is described as follow:

Manufacturing Sample A of the Present Invention.

Sample A is manufactured according to the first manufacturing procedure.A modified carbonaceous electrode 30 is obtained via the firstmanufacturing procedure. Two of the modified carbonaceous electrodes 30are then combined with a solid polymer electrolyte 40. The solid polymerelectrolyte 40 is placed between the two modified carbonaceouselectrodes 30. Wherein the solid polymer electrolyte 40 and the twomodified carbonaceous electrodes 30 are pressed together to form a supercapacitor 10.

The solid polymer electrolyte 40 of the present invention belongs to theSulfonated polyether ether ketone (SPEEK) family. The SPEEK is dissolvedin Dimethyl sulfoxide (DMSO) to form a SPEEK solution. The SPEEKsolution is first spread onto a flat glass and then baked to form amembrane of the solid polymer electrolyte. The membrane of the solidpolymer electrolyte can be torn off from the flat glass and serve as thesolid polymer electrolyte 40 of the super capacitor 10. Wherein thethickness of the solid polymer electrolyte 40 is 30 μm.

The SPEEK solution may also be used to prepare the active material 32.For example, the SPEEK solution can serve as an adhesive to evenlycombine 85 wt % of a main component (activated carbon) and 5 wt % ofconductivity additive (carbon black, brand name XC-72R) to form a slurryof the active material 32. The solid part of the slurry includes 85 wt %of activated carbon, 5 wt % carbon black, and 10 wt % SPEEK. The slurrycan be spread onto the conductive carbonaceous material 31 to obtain themodified carbonaceous electrode 30.

Referring to FIG. 5, the manufacture of the conductive carbonaceousmaterial 31 is based on the U.S. Pat. No. 7,670,970 B2 and U.S. Pat. No.7,927,575 B2. The slurry is distributed onto the conductive carbonaceousmaterial 31. Wherein part of the slurry will cover the surface of theconductive carbonaceous material 31 and the rest of the slurry willpermeate into the conductive carbonaceous material 31 to cover theentire surface of every carbon fiber of the conductive carbonaceousmaterial 31. The conductive carbonaceous material 31 covered with theslurry is then baked at 120° C. and forms the modified carbonaceouselectrode 30. The dimension of the modified carbonaceous electrode 30 is2 cm×2 cm, and contains 5 mg of activated carbon. Finally, spray DMSOsolution onto the two surfaces of the SPEEK solid polymer electrolyte 40and place the SPEEK solid polymer electrolyte 40 between two of themodified carbonaceous electrode 30. After that, perform a press-fitprocedure to combine the modified carbonaceous electrode 30 and theSPEEK solid polymer electrolyte 40 in order to obtain the supercapacitor 10.

Manufacturing Sample B Using Traditional Electrodes.

Sample B is the control group in reference to Sample A. Referring toFIG. 2, the manufacturing of Sample B is the same as that of Sample Aexcept that Sample B employs traditional electrodes instead of themodified carbonaceous electrode 30. The purpose of Sample B is tocompare the effect traditional electrode and the modified carbonaceouselectrode 30. The traditional electrode uses the same active material 32as Sample A (85 wt % of activated carbon, 5 wt % of carbon black, 10 wt% SPEEK) and the active material 32 is spread onto the surface of acopper-foil current collector. The area covered with the active material32 is 2 cm×2 cm. The active material 32 is solidified after baking andthe traditional electrode is ready. Each of the traditional electrodescontains 5 mg of activated carbon. The manufacture of the SPEEK solidpolymer electrolyte membrane is the same as described in Sample A. TheSPEEK solid polymer electrolyte membrane is placed between two of thetraditional electrodes, wherein the traditional electrodes and the SPEEKsolid polymer electrolyte membrane are combined via press-fit process toobtain Sample B.

FIG. 8 is the current-voltage diagram (CV diagram) of the supercapacitor 10 comprising Sample A and the super capacitor 10 comprisingSample B. The super capacitor 10 of this present invention shows to bebetter than super capacitors using traditional electrodes under a 50mV/s scanning frequency. Wherein the capacitance density of Sample A andSample B is 1.5 F/cm² and 0.89 F/cm² respectively. Furthermore, Sample Ahas a high electrical power ratio density of 4.0 kW/kg, and a highenergy density of 20 Wh/kg. This result clearly shows that the supercapacitor 10 comprising the modified carbonaceous electrode 30 performsbetter than the super capacitor 10 comprising traditional electrode.

FIG. 9 shows the thermo gravimetric analysis (TGA) of Sample A. 500 mgof the modified carbonaceous electrode 30 was taken out for the thermogravimetric analysis. The TGA result was further calculated under firstdegree differential analysis. The result shows that thermal degradationpeak occurs at high temperatures includes 210° C., 381° C., and 528° C.There is no thermal degradation peak lower that 200° C., which indicatesthat the modified carbonaceous electrode 30 and the solid polymerelectrolyte are stable at high temperature. Therefore, the supercapacitor 10 is a safe energy storage device that can be used undercritical temperature. The thermal stability of the super capacitor 10 ismuch better than traditional super capacitors using water-basedelectrolytes (working temperature<100° C.), liquid-state organic andgel-like electrolytes (working temperature<150° C.).

Manufacturing of Sample C.

Sample C is an asymmetric super capacitor, wherein the cathode is anon-Faradaic electrode and the anode is a Faradaic electrode. The SPEEKsolid polymer electrolyte 40 is manufactured according to the sameprocedure as mentioned in the making of Sample A. The thickness of theSPEEK solid polymer electrolyte 40 used in Sample C is 60 μm. The SPEEKsolution may also be used as adhesives as described in the preparationof Sample A, wherein the slurry prepared serves as the active material32 for the cathode. The cathode slurry is distributed on the surface ofthe conductive carbonaceous material 31 as illustrated in thepreparation of Sample A. The size of the modified carbonaceous electrode30 is also 2 cm×2 cm, and the main component of the active material 32is 5 mg activated carbon.

Furthermore, the SPEEK is used as adhesive to prepare an anode slurry asthe active material 32 comprising 10 wt % SPEEK, 80 wt % of the maincomponent (which is Polymethylthiophene in this embodiment), and 5 wt %of conductivity additive (which is carbon black in this embodiment). Theanode slurry is distributed on another conductive carbonaceous material31, wherein the conductive carbonaceous material 31 is producedaccording to the first manufacturing procedure. The other modifiedcarbonaceous electrode 30 serves as the anode is obtained after baking.The main component of the active material 32 here contains 5 mg ofPolymethylthiophene. Finally, place the SPEEK solid polymer electrolyte40 between the cathode and the anode, then combine the electrodes andthe electrolyte together by press-fit process and obtain the asymmetricsuper capacitor 10.

Sample C has passed the Constant Current Charge Discharge test (CCCDtest) for the charge and discharge of currents between 0-3V. The resultis shown in FIG. 10. The test is conducted with a single unit not inseries. The charge and discharge current density is 10 mA/cm². The studyshows that the super capacitor of this invention can still charge anddischarge normally even at high voltage such as 3.0V. This result ismuch higher than that the rated voltage (V_(R)) of currently knowncommercial water-based electrolytes (which normally has a V_(R) of1.0-1.7V) and currently known commercial organic electrolytes (which hasa V_(R) of 2.5-2.7V).

Manufacturing of Sample D.

Sample D uses copolymer to produce solid polymer electrolyte 40. First,dissolve 5 wt % of Polyvinyl (PVA) and 95 wt % of SPEEK into DMSO toprepare a PVA-SPEEK solution. Spread the PVA-SPEEK solution onto a flatglass and then send for baking to solidify PVA-SPEEK. A PVA-SPEEK solidcopolymer electrolyte membrane can be torn off the flat glass afterbaking and serves as the solid polymer electrolyte 40 as shown in FIG.2. The thickness of the solid polymer electrolyte 40 is 50 μm in SampleD. PVA-SPEEK solution is also used to produce the active material 32.Wherein PVA-SPEEK solution is used as adhesive (10 wt % of the activematerial 32 is PVA-SPEEK) to combine 85 wt % of activated carbon and 5wt % of carbon black in order to obtain a slurry of the active material32. The slurry is then distributed onto the conductive carbon fiberproduced according to the second manufacturing procedure. The conductivecarbon fiber covered with the slurry is baked at 140° C. and weaved in atwo-dimensional manner to form the modified carbonaceous electrode 30.The size of the electrode is 2 cm×2 cm and the amount of the activatedcarbon is 5 mg. Finally, place the PVA-SPEEK copolymer electrolyte 40membrane between two of the modified carbonaceous electrode 30 andundergo a press-fit procedure to combine the electrodes and theelectrolyte in order to obtain the super capacitor 10.

The result of the Cyclic life test of Sample D is shown in FIG. 11. Thetest is conducted under a constant current density of 10 mA/cm². Thestudy shows that the before the test is 220 F/g, and it slightlydecreased to 214 F/g after 120000 times of test cycles. The decline rateis less than 3% and there is no obvious decrease in the performance offunctions.

What is claimed is:
 1. A method of manufacturing a super capacitor,comprising: preparing an ion-conducting polymer; dissolving theion-conducting polymer in an organic solvent to obtain an ion-conductingpolymer solution; spreading the ion-conducting polymer solution on asmooth plate then sending for baking and tearing off a solid-statepolymer electrolyte after the baking process ends; mixing an adhesive, aconductivity additive, and a main component to form an active material;spreading the active material on a first conductive carbonaceousmaterial and a second conductive carbonaceous material, wherein thefirst conductive carbonaceous material and the second conductivecarbonaceous material each comprises a carbon fiber having a resistivitylower than 5×10⁻² Ω/cm, a density greater than 1.6 g/cm³, and a carboncontent greater than 65 wt %; baking the first conductive carbonaceousmaterial and the second conductive carbonaceous material, both arecovered with the active material, to obtain a first modifiedcarbonaceous electrode and a second modified carbonaceous electroderespectively; pressing the first modified carbonaceous electrode, thesolid-state polymer electrolyte, and the second modified carbonaceouselectrode in a sandwich-like structure to obtain a super capacitor; andinstalling a first conductive pad and a second conductive pad on thefirst modified carbonaceous electrode and the second modifiedcarbonaceous electrode respectively.
 2. The method of claim 1, whereinthe first conductive carbonaceous material and the second conductivecarbonaceous material each further comprises a carbon cloth, a carbonfelt, a carbon paper, a carbon pellet, or a carbon powder.
 3. The methodof claim 1, wherein the ion-conducting polymer is made of one selectedfrom the group consisting of polyether ether ketone, sulfonatedpolyether ether ketone, polyphenylene vinylene, poly(ether ketoneketone), polyethylene oxide, polyvinyl alcohol, polytetrafluoroethylene,polyethylenedioxythiophene, polyaniline, polypyrrole, and thecombination thereof.
 4. The method of claim 1, wherein the step ofspreading the active material solution is performed in a processselecting from the group consisting of painting, tape casting, pressing,spraying, immersing, and the combination thereof.
 5. The method of claim1, the modified carbonaceous electrode is made by weaving the carbonfiber in a process selecting from the group consisting of needlepunching, papermaking process, and the combination thereof.
 6. A methodof manufacturing a super capacitor, comprising: mixing an adhesive, aconductivity additive, and a main component to form an active material;immersing a first conductive carbonaceous material and a secondconductive carbonaceous material into the active material, wherein thefirst conductive carbonaceous material and the second conductivecarbonaceous material each contains a carbon fiber having a resistivitylower than 5×10⁻² Ω/cm, a density greater than 1.6 g/cm³, and a carboncontent greater than 65 wt %; drying the active material in the firstconductive carbonaceous material and the second conductive carbonaceousmaterial to obtain a first modified carbonaceous electrode and a secondmodified carbonaceous electrode; providing a solid-state polymerelectrolyte; combining the first modified carbonaceous electrode, thesolid-state polymer electrolyte, and the second carbonaceous electrodesequentially in a sandwich-like structure; and configuring a firstconductive pad and a second conductive pad to the first modifiedcarbonaceous electrode and the second modified carbonaceous electroderespectively.
 7. The method of claim 6, wherein the adhesive is oneselected from the group consisting of polyether ether ketone, sulfonatedpolyether ether ketone, polyphenylene vinylene, poly(ether ketoneketone), polyethylene oxide, polyvinyl alcohol, polytetrafluoroethylene,polyethylenedioxythiophene, polyaniline, polypyrrole, and thecombination thereof.
 8. The method of claim 6, wherein the conductivityadditive is a carbon black, a graphene, or a carbon nanotube.
 9. Themethod of claim 6, wherein the main component is an activated carbonpowder with a specific surface area between 20 and 2000 m²/g.
 10. Themethod of claim 6, wherein the main component is one selected from thegroup consisting of polyether ether ketone, sulfonated polyether etherketone, polyphenylene vinylene, poly(ether ketone ketone), polyethyleneoxide, polyvinyl alcohol, polytetrafluoroethylene,polyethylenedioxythiophene, polyaniline, polypyrrole, and thecombination thereof.
 11. The method of claim 6, wherein the maincomponent is a metal oxide powder selected from the group consisting ofruthenium dioxide, titanium dioxide, magnesium dioxide, zinc oxide,nickel oxide, iridium dioxide, and the combination thereof.
 12. Themethod of claim 6, wherein the first conductive carbonaceous materialand the second conductive carbonaceous material each has a sheetresistance of less than 200 Ω/sq, a density greater than 1.6 g/cm³, anda carbon content of greater than 65 wt %.
 13. The method of claim 6,wherein the first conductive carbonaceous material and the secondconductive carbonaceous material each has a specific surface arearanging from 20 m²/g to 2000 m²/g.
 14. The method of claim 6, whereinthe active material is distributed within the vacant spaces and on thesurfaces of the first conductive carbonaceous material and the secondconductive carbonaceous material.
 15. The method of claim 6, wherein thefirst conductive carbonaceous material and the second conductivecarbonaceous material each further contains a carbon cloth, a carbonfelt, a carbon paper, a carbon pellet, or a carbon powder.
 16. Themethod of claim 6, wherein the step of providing the solid-state polymerelectrolyte comprises the sub-steps of: dissolving an ion-conductingpolymer in an organic solvent to obtain an ion-conducting polymersolution; applying the ion-conducting polymer solution onto a plate; anddrying the ion-conducting polymer solution on the plate to obtain thesolid-state polymer electrolyte.
 17. The method of claim 16, wherein thethickness of the solid-state polymer electrolyte is ranging from 0.5 μmto 50 μm.
 18. The method of claim 6, wherein the step of drying isperformed under a temperature between 60° C. and 400° C.